US4376715A - Composition based on liquid crystal for electro-optical device - Google Patents
Composition based on liquid crystal for electro-optical device Download PDFInfo
- Publication number
- US4376715A US4376715A US06/172,641 US17264180A US4376715A US 4376715 A US4376715 A US 4376715A US 17264180 A US17264180 A US 17264180A US 4376715 A US4376715 A US 4376715A
- Authority
- US
- United States
- Prior art keywords
- sub
- formula
- group
- substituted
- liquid crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 34
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 anthraquinone compound Chemical class 0.000 claims description 8
- KIJUYOHUDBTXOU-UHFFFAOYSA-N 1,5-diamino-2-(4-butoxyphenyl)-4,8-dihydroxyanthracene-9,10-dione Chemical compound C1=CC(OCCCC)=CC=C1C1=CC(O)=C(C(=O)C=2C(=C(O)C=CC=2N)C2=O)C2=C1N KIJUYOHUDBTXOU-UHFFFAOYSA-N 0.000 claims description 3
- IDVXRDUZRKICBX-UHFFFAOYSA-N 4,8-diamino-2,6-bis(4-butoxyphenyl)-1,5-dihydroxyanthracene-9,10-dione Chemical compound C1=CC(OCCCC)=CC=C1C1=CC(N)=C(C(=O)C=2C(=C(N)C=C(C=2O)C=2C=CC(OCCCC)=CC=2)C2=O)C2=C1O IDVXRDUZRKICBX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 150000004056 anthraquinones Chemical class 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 abstract description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000004150 EU approved colour Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IIHQNAXFIODVDU-UHFFFAOYSA-N pyrimidine-2-carbonitrile Chemical class N#CC1=NC=CC=N1 IIHQNAXFIODVDU-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001000 anthraquinone dye Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- CUIHODIOWPLCMG-UHFFFAOYSA-N 1,5-dihydroxy-4,8-dinitroanthracene-9,10-dione Chemical compound O=C1C2=C(O)C=CC([N+]([O-])=O)=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2O CUIHODIOWPLCMG-UHFFFAOYSA-N 0.000 description 1
- KITDWGXKROZQAP-UHFFFAOYSA-N 2-phenylheptanenitrile Chemical compound CCCCCC(C#N)C1=CC=CC=C1 KITDWGXKROZQAP-UHFFFAOYSA-N 0.000 description 1
- JGTFEALFWCXWCO-UHFFFAOYSA-N 4,8-diamino-7-(4-butoxyphenyl)-1,5-dihydroxy-9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC(OCCCC)=CC=C1C1=CC(O)=C(C(=O)C=2C(=C(O)C(=CC=2N)S(O)(=O)=O)C2=O)C2=C1N JGTFEALFWCXWCO-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229940126543 compound 14 Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001916 cyano esters Chemical class 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WSALIDVQXCHFEG-UHFFFAOYSA-L disodium;4,8-diamino-1,5-dihydroxy-9,10-dioxoanthracene-2,6-disulfonate Chemical compound [Na+].[Na+].O=C1C2=C(N)C=C(S([O-])(=O)=O)C(O)=C2C(=O)C2=C1C(O)=C(S([O-])(=O)=O)C=C2N WSALIDVQXCHFEG-UHFFFAOYSA-L 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- UHOKSCJSTAHBSO-UHFFFAOYSA-N indanthrone blue Chemical compound C1=CC=C2C(=O)C3=CC=C4NC5=C6C(=O)C7=CC=CC=C7C(=O)C6=CC=C5NC4=C3C(=O)C2=C1 UHOKSCJSTAHBSO-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- CSMWJXBSXGUPGY-UHFFFAOYSA-L sodium dithionate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)S([O-])(=O)=O CSMWJXBSXGUPGY-UHFFFAOYSA-L 0.000 description 1
- 229940075931 sodium dithionate Drugs 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/60—Pleochroic dyes
- C09K19/603—Anthroquinonic
Definitions
- the invention relates to liquid-crystal-based compositions for use in electro-optical devices and more particularly in display arrangements.
- such a dye must have a high order parameter "S"--this parameter corresponding to the measure of the power of orientation of the dye by the molecules of the liquid crystal--for a display with a strong contrast to be obtained.
- the basic structure of the compounds envisaged must of course correspond to a colour appropriate for use in a display arrangement, preferably blue and red.
- the first dyes used in liquid crystals were azoic dyes or derivatives thereof, as disclosed particularly by D. L. White and G. N. Taylor, J. Appl. Phys. 45, 4718 (1974), by A. Bloom et al., Mol. Cryst. Liq. Cryst. Letters 41, 1 (1977) and by J. Constant et al., Elec. Letters, 12, 514 (1976). These compounds generally have a relatively high order parameter. On the other hand, most of them do not have an appropriate maximum absorption wavelength, and in particular azoic dyes are not sufficiently stable to light, so they cannot be considered for use in manufacturing commercial liquid-crystal displays.
- the invention is based inter alia on the discovery that basic anthraquinone structures, with an NH 2 or OH group in position 1, have a higher order parameter when a side chain is substituted on the anthraquinone ring in position 2 or positions 2 and 6, or respectively in position 3 or positions 3 and 7.
- the present invention provides a composition based on liquid crystal and designed for use in an electro-optical device, particularly a display arrangement, and containing as pleochroic dye an anthraquinone compound represented by general formula (I) ##STR4## where R 1 is a substituted or unsubstituted amino group or a hydroxy group; each of R 2 , R 3 and R 4 , which are identical or different, is a hydrogen atom, a substituted or unsubstituted amino group, a hydroxy group or a nitro group; R is a hydrogen or halogen atom or a hydroxy, lower alkyl or lower alkoxy group; n is 1, 2, 3 or 4, the Rs being identical or different when n is 2, 3 or 4; X is a hydrogen or halogen atom, a hydroxy or mercapto group, a straight, branched or cyclic C 1-16 alkyl radical, a substituted or unsubstituted aryl group or a group of formula ##
- Such compounds have a good stability to light.
- formula (I) dye with a side chain in position 2 (or still better, two side chains), of the alkoxyphenyl type, has a good order parameter in a mixture of liquid crystals based on biphenyl, phenylcyclohexane or pyrimidine, it is not the same with a mixture based on esters.
- Swiss patent (application No. 8863/79 of 10.2.1979) describes a class of very stable anthraquinone compounds where the order parameter is approximately 0.60 to 0.65. They comprise the same basic structure of formula (II) as mentioned above, substituted in position 2 or 3 by a side chain similar to that defined for the composition of formula (I) of the present invention, except that the side chain is joined to the anthraquinone ring through the agency of an oxygen atom. Examination of the molecular model of such a compound shows that the angle of 120° formed by the two bonds of the oxygen bridge does not allow the molecule to take on an ideal elongated shape (see diagram below). This is reflected in the values of the order parameter in the liquid crystal, which are relatively low. ##STR8##
- the absence of the oxygen bridge enables the order parameter to be increased from 0.60-0.65 to 0.65-0.70.
- the stability of the compound without any --O-- bridge is not substantially different from that with such an --O-- bridge, and yet is perfectly adequate for use in solution in a liquid crystal for a display arrangement; this stability is in any case far greater than that of other types of colouring agents with a comparable order parameter.
- a saturated solution of each of compounds 1 to 19 is prepared in a liquid crystal, and the solution obtained is filtered, 100 ⁇ l of the filtrate is taken out and dissolved in 50 cc of chloroform.
- optical density of each solution is measured spectroscopically, and the concentration of the dye at saturation is deducted from the reading, the coefficient of absorption being known in chloroform.
- a 0.5% solution of each of compounds 1 to 19 in a liquid crystal is placed in a glass cell 30 ⁇ thick, coated with an aligning film (tangentially evaporated SiO x or polished polyimide).
- the optical density of each of the solutions is then measured at its maximum absorption in polarised light, firstly when the direction of the polariser is parallel with (D.sub. ⁇ ) and secondly when it is perpendicular to (D.sub. ⁇ ) the direction of alignment.
- the order parameter is calculated from the following equation: ##EQU1## where r is the dichroic ratio corresponding to the ratio ##EQU2##
- Table II The results obtained have also been set out in Table II below. It will be seen from Table II that the values of the order parameter (S) varies according to the liquid crystal used for the measurement.
- a glass cell similar to that used in determining the order parameter, and containing a solution of each of the above mentioned compounds in a liquid crystal, is subjected to radiation from a "Xenon" lamp, filtered so as to reconstitute solar illumination at mid-day in our latitudes (Leybold Heraeus Sun Test).
- the thickness of the cell and the concentration of each solution are adjusted to bring the optical density close to 1, and the time taken for the optical density to reach half its initial value is measured.
- the formula (I) compounds in Table II all have a half life of over 1000 hours. This is perfectly adequate in practice for use as liquid crystal dyes intended for display cells, e.g. for watches or measuring instruments.
- the formula (I) compounds which can be used as dyes in solution in liquid crystals for display devices may be prepared by conventional methods of synthesising anthraquinone compounds, for example as described by K. Venkataraman et al., Indian Journal of Chemistry, 9, 1060 (1971).
- the suspension obtained is heated on reflux for 4 hours to destroy the boric ester, and a violet precipitate is filtered off after cooling, corresponding to 4,8-diamino-1,5-dihydroxy-3-p-butoxyphenyl-anthraquinone-6-sulphonic acid.
- the moist precipitate is dissolved hot in a mixture of 24 ml of 33% ammonia and 160 ml of water, and the sulphonic groups are separated by adding 2.2 g of sodium dithionate in stages.
- the mixture is finally heated to 95° C. for approximately 2 hours, then cooled and filtered.
- the precipitate thus obtained is washed with slightly acidified water, then with a great excess of water, and dried.
- the desired product may further be purified by crystallisation or chromatography if necessary.
- 10 g of the crude product thus obtained is then reduced by heating it to boiling point for 2 hours in a solution containing 50.0 g of sodium sulphide, 250 ml of water and 32 ml of ethanol.
- the mixture is filtered hot and the precipitate recovered is washed with water until neutral.
- the moist precipitate is further heated to boiling point with 300 ml of 10 % hydrochloric acid, filtered, washed until neutral, and dried.
- the desired product (compound No. 14) may further be purified by crystallisation or chromatography if necessary.
- a single type of liquid crystal may be used, or preferably a mixture of liquid crystals such as those marketed e.g. by BDH Chemicals Limited under references E3, E7, E8 or E9 (the respective compositions being mentioned in published European patent application No. 78300487.2) or by Hoffmann-La-Roche under references ROTN-103 or ROTN 404.
- the liquid crystals should preferably be neumatic with positive or negative anisotropy, and may or may not contain an optically active agent in addition.
- composition according to the invention may further comprise two or more formula (I) dyes or possibly other types of anthraquinone dyes, as well as a cholesterising agent and/or an aligning agent.
- the cholesterising agent may be the one known from BDH Chemicals Limited under reference "CB 15", which is preferably added in a quantity of about 3% of the total composition.
- the aligning agent designed to disperse the molecules of the liquid crystals perpendicularly to walls of the electro-optical device may be approximately 2% of a surfactant, for example a sorbitol monoester, sorbitol monolaurate being particularly suitable.
- the pleochroic dye of formula (I) is generally present in the composition of the invention in a quantity corresponding to about 0.5 to 5% of the total composition, e.g. preferably about 1.5%.
- compositions according to the invention are mentioned in the following Table IV, which allow the realization for example of a watch digital display working at 4.5 V and with a thickness of 8 ⁇ m.
- the appropriate dye concentration is determined depending on the aimed appearance and taking accoung of the cell thickness, whereas the cholesterising agent concentration "CB15" is such that the pitch of the induced cholesteric helix corresponds to the used thickness.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH7543/79 | 1979-08-17 | ||
| CH754379A CH641828A5 (fr) | 1979-08-17 | 1979-08-17 | Composition a base de cristal liquide pour dispositif electro-optique. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4376715A true US4376715A (en) | 1983-03-15 |
Family
ID=4326791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/172,641 Expired - Lifetime US4376715A (en) | 1979-08-17 | 1980-07-25 | Composition based on liquid crystal for electro-optical device |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4376715A (enrdf_load_stackoverflow) |
| JP (1) | JPS5632578A (enrdf_load_stackoverflow) |
| CH (1) | CH641828A5 (enrdf_load_stackoverflow) |
| DE (1) | DE3028593C2 (enrdf_load_stackoverflow) |
| FR (1) | FR2463799A1 (enrdf_load_stackoverflow) |
| GB (1) | GB2061994B (enrdf_load_stackoverflow) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4428858A (en) | 1979-10-02 | 1984-01-31 | Ebauches S.A. | Composition based on liquid crystal for electro-optical device |
| US4456545A (en) * | 1980-10-24 | 1984-06-26 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Dichroitic anthraquinone dyestuffs useful in liquid crystalline dielectrics and electro-optical indicator elements |
| US4466899A (en) * | 1981-01-10 | 1984-08-21 | Basf Aktiengesellschaft | Dyes for use in liquid crystal mixtures |
| US4472292A (en) * | 1981-07-02 | 1984-09-18 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid crystalline dielectric, new dichroitic naphthoquinone dyestuffs and electro-optical indicator element |
| US4473486A (en) * | 1979-03-16 | 1984-09-25 | Mitsui Toatsu Chemicals, Inc. | Composition for liquid crystal color display elements |
| US4478739A (en) * | 1982-07-16 | 1984-10-23 | Asulab S.A. | Dark colored composition based on liquid crystals |
| US4483593A (en) * | 1981-03-20 | 1984-11-20 | Hitachi, Ltd. | Guest-host type liquid crystal composition and liquid crystal display device |
| US4483594A (en) * | 1980-07-29 | 1984-11-20 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Liquid crystal materials containing pleochroic anthraquinone dyes |
| US4491532A (en) * | 1980-09-30 | 1985-01-01 | Siemens Aktiengesellschaft | Liquid-crystal mixture with a pleochroic anthraquinone dye, and method for producing such a dye |
| US4495083A (en) * | 1979-10-12 | 1985-01-22 | Hitachi, Ltd. | Guest-host type liquid crystal composition and liquid crystal display device using the same |
| US4499004A (en) * | 1982-01-28 | 1985-02-12 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid crystal dielectrics, new dyestuffs useful therein, processes for their preparation, and electrooptical display elements based thereon |
| US4505549A (en) * | 1981-01-12 | 1985-03-19 | Sumitomo Chemical Company, Limited | Liquid crystal display device |
| US4530572A (en) * | 1982-12-30 | 1985-07-23 | Minnesota Mining And Manufacturing Company | Substituted anthraquinone-type isotropic dyes for liquid crystal display devices |
| US4532069A (en) * | 1982-12-24 | 1985-07-30 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Anthraquinone dyestuffs for liquid crystal dielectrics |
| US4536320A (en) * | 1980-01-17 | 1985-08-20 | Mitsui Toatsu Chemicals, Inc. | Nematic liquid crystalline composition |
| US4551265A (en) * | 1979-09-20 | 1985-11-05 | Bayer Aktiengesellschaft | Fluorescent dyestuffs, processes for their preparation and their use as laser dyestuffs |
| US4585574A (en) * | 1980-12-12 | 1986-04-29 | Bayer Aktiengesellschaft | Anthraquinone dyestuffs, processes for their preparation, their use, and liquid-crystalline materials containing anthraquinone dyestuffs |
| EP0181601A1 (de) * | 1984-11-16 | 1986-05-21 | Bayer Ag | Flüssigkristallines Material |
| US4689171A (en) * | 1982-05-03 | 1987-08-25 | Bayer Aktiengesellschaft | Anthraquinone dyestuffs, their preparation and use and dichroic material containing these anthraquinone dyestuffs |
| US4808080A (en) * | 1986-07-22 | 1989-02-28 | Electric Power Research Institute | Flow coupler assembly for double-pool-type reactor |
| US4952678A (en) * | 1986-11-15 | 1990-08-28 | Basf Aktiengesellschaft | Trisazo dyes |
| US20140173893A1 (en) * | 2011-08-31 | 2014-06-26 | Jsr Corporation | Method for producing liquid crystal display, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal device |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4304683A (en) * | 1979-03-16 | 1981-12-08 | Mitsui Toatsu Chemicals, Inc. | Composition for liquid crystal color display element |
| DE3007198A1 (de) * | 1980-02-26 | 1981-09-03 | Siemens AG, 1000 Berlin und 8000 München | Pleochroitischer anthrachinon-farbstoff, verfahren zu seiner herstellung und verwendung des farbstoffs |
| DE3014933A1 (de) * | 1980-04-18 | 1981-10-29 | Bayer Ag, 5090 Leverkusen | Fluessigkristalline materialien enthaltend anthrachinonfarbstoffe |
| EP0043904A3 (de) * | 1980-07-10 | 1982-03-31 | F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft | Farbstoffhaltige Mischungen, neue Farbstoffe und deren Verwendung in Flüssigkristallmischungen |
| US4405211A (en) * | 1980-07-29 | 1983-09-20 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Liquid crystal compositions with pleochroic anthraquinone dyes |
| GB2095273B (en) * | 1980-07-31 | 1984-09-19 | Ivashchenko Aleksandr Vasilevi | Derivatives of 2,2'-azoimidazole method for the preparation thereof liquid crystal material and electro-optical device |
| JPS5755984A (en) * | 1980-09-22 | 1982-04-03 | Hitachi Ltd | Liquid crystal composition |
| DE3036896A1 (de) * | 1980-09-30 | 1982-04-15 | Siemens AG, 1000 Berlin und 8000 München | Fluessigkristallgemisch mit einem pleochroitischen anthrachinon-farbstoff und verfahren zur herstellung eines solchen farbstoffes |
| GB2094825B (en) * | 1981-01-17 | 1984-09-12 | Mitsubishi Chem Ind | Liquid crystal compositions containing pleochroic anthraquinone dyes |
| JPS5825381A (ja) * | 1981-08-08 | 1983-02-15 | Nippon Kanko Shikiso Kenkyusho:Kk | 液晶組成物 |
| DE3137298A1 (de) * | 1981-09-18 | 1983-04-14 | Bayer Ag, 5090 Leverkusen | Anthrachinonfarbstoffe |
| JPS5876482A (ja) * | 1981-10-30 | 1983-05-09 | Alps Electric Co Ltd | 液晶混合物 |
| JPS58109580A (ja) * | 1981-12-24 | 1983-06-29 | Alps Electric Co Ltd | カラ−液晶表示素子 |
| JPS58109578A (ja) * | 1981-12-24 | 1983-06-29 | Alps Electric Co Ltd | カラ−液晶表示素子 |
| JPS58109579A (ja) * | 1981-12-24 | 1983-06-29 | Alps Electric Co Ltd | カラ−液晶表示素子 |
| JPS58111882A (ja) * | 1981-12-25 | 1983-07-04 | Alps Electric Co Ltd | カラ−液晶表示装置 |
| FR2627864A1 (fr) * | 1988-02-29 | 1989-09-01 | Asulab Sa | Dispositif d'affichage pour instrument de mesure |
| FR2743924B1 (fr) | 1996-01-23 | 1998-05-22 | Asulab Sa | Dispositif d'affichage d'un decor et piece d'horlogerie le comprenant |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549667A (en) * | 1962-01-12 | 1970-12-22 | Bayer Ag | Preparation of aryl substituted hydroxy anthraquinones |
| US3792970A (en) * | 1971-04-14 | 1974-02-19 | Bayer Ag | Exhaustion process for dyeing synthetic fibre materials |
| US4014906A (en) * | 1974-12-20 | 1977-03-29 | Ciba-Geigy Corporation | Process for the manufacture of anthraquinone compounds |
| US4111966A (en) * | 1975-12-23 | 1978-09-05 | Ciba-Geigy Corporation | 1,5-Dihydroxy-4,8-diamino-anthraquinone compounds arylated in 3-position |
| US4210413A (en) * | 1977-04-02 | 1980-07-01 | Bayer Aktiengesellschaft | Transfer printing process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54134452A (en) * | 1978-04-10 | 1979-10-18 | Hitachi Ltd | Quest-host type liquid crystal display device |
| JPS54157786A (en) * | 1978-05-23 | 1979-12-12 | Minnesota Mining & Mfg | Multiicoloring dyestuff and photoelectric display device |
-
1979
- 1979-08-17 CH CH754379A patent/CH641828A5/fr not_active IP Right Cessation
-
1980
- 1980-07-24 FR FR8016622A patent/FR2463799A1/fr active Granted
- 1980-07-25 US US06/172,641 patent/US4376715A/en not_active Expired - Lifetime
- 1980-07-28 DE DE3028593A patent/DE3028593C2/de not_active Expired
- 1980-08-13 JP JP11043880A patent/JPS5632578A/ja active Pending
- 1980-08-14 GB GB8026521A patent/GB2061994B/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3549667A (en) * | 1962-01-12 | 1970-12-22 | Bayer Ag | Preparation of aryl substituted hydroxy anthraquinones |
| US3792970A (en) * | 1971-04-14 | 1974-02-19 | Bayer Ag | Exhaustion process for dyeing synthetic fibre materials |
| US4014906A (en) * | 1974-12-20 | 1977-03-29 | Ciba-Geigy Corporation | Process for the manufacture of anthraquinone compounds |
| US4111966A (en) * | 1975-12-23 | 1978-09-05 | Ciba-Geigy Corporation | 1,5-Dihydroxy-4,8-diamino-anthraquinone compounds arylated in 3-position |
| US4210413A (en) * | 1977-04-02 | 1980-07-01 | Bayer Aktiengesellschaft | Transfer printing process |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4473486A (en) * | 1979-03-16 | 1984-09-25 | Mitsui Toatsu Chemicals, Inc. | Composition for liquid crystal color display elements |
| US4551265A (en) * | 1979-09-20 | 1985-11-05 | Bayer Aktiengesellschaft | Fluorescent dyestuffs, processes for their preparation and their use as laser dyestuffs |
| US4428858A (en) | 1979-10-02 | 1984-01-31 | Ebauches S.A. | Composition based on liquid crystal for electro-optical device |
| US4495083A (en) * | 1979-10-12 | 1985-01-22 | Hitachi, Ltd. | Guest-host type liquid crystal composition and liquid crystal display device using the same |
| US4536320A (en) * | 1980-01-17 | 1985-08-20 | Mitsui Toatsu Chemicals, Inc. | Nematic liquid crystalline composition |
| US4483594A (en) * | 1980-07-29 | 1984-11-20 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Liquid crystal materials containing pleochroic anthraquinone dyes |
| US4491532A (en) * | 1980-09-30 | 1985-01-01 | Siemens Aktiengesellschaft | Liquid-crystal mixture with a pleochroic anthraquinone dye, and method for producing such a dye |
| US4456545A (en) * | 1980-10-24 | 1984-06-26 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Dichroitic anthraquinone dyestuffs useful in liquid crystalline dielectrics and electro-optical indicator elements |
| US4585574A (en) * | 1980-12-12 | 1986-04-29 | Bayer Aktiengesellschaft | Anthraquinone dyestuffs, processes for their preparation, their use, and liquid-crystalline materials containing anthraquinone dyestuffs |
| US4466899A (en) * | 1981-01-10 | 1984-08-21 | Basf Aktiengesellschaft | Dyes for use in liquid crystal mixtures |
| US4505549A (en) * | 1981-01-12 | 1985-03-19 | Sumitomo Chemical Company, Limited | Liquid crystal display device |
| US4483593A (en) * | 1981-03-20 | 1984-11-20 | Hitachi, Ltd. | Guest-host type liquid crystal composition and liquid crystal display device |
| US4472292A (en) * | 1981-07-02 | 1984-09-18 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid crystalline dielectric, new dichroitic naphthoquinone dyestuffs and electro-optical indicator element |
| US4499004A (en) * | 1982-01-28 | 1985-02-12 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid crystal dielectrics, new dyestuffs useful therein, processes for their preparation, and electrooptical display elements based thereon |
| US4689171A (en) * | 1982-05-03 | 1987-08-25 | Bayer Aktiengesellschaft | Anthraquinone dyestuffs, their preparation and use and dichroic material containing these anthraquinone dyestuffs |
| US4478739A (en) * | 1982-07-16 | 1984-10-23 | Asulab S.A. | Dark colored composition based on liquid crystals |
| US4532069A (en) * | 1982-12-24 | 1985-07-30 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Anthraquinone dyestuffs for liquid crystal dielectrics |
| US4530572A (en) * | 1982-12-30 | 1985-07-23 | Minnesota Mining And Manufacturing Company | Substituted anthraquinone-type isotropic dyes for liquid crystal display devices |
| EP0181601A1 (de) * | 1984-11-16 | 1986-05-21 | Bayer Ag | Flüssigkristallines Material |
| US4808080A (en) * | 1986-07-22 | 1989-02-28 | Electric Power Research Institute | Flow coupler assembly for double-pool-type reactor |
| US4952678A (en) * | 1986-11-15 | 1990-08-28 | Basf Aktiengesellschaft | Trisazo dyes |
| US20140173893A1 (en) * | 2011-08-31 | 2014-06-26 | Jsr Corporation | Method for producing liquid crystal display, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal device |
| US9447323B2 (en) * | 2011-08-31 | 2016-09-20 | Jsr Corporation | Method for producing liquid crystal display |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3028593C2 (de) | 1982-11-04 |
| FR2463799B1 (enrdf_load_stackoverflow) | 1984-06-08 |
| GB2061994A (en) | 1981-05-20 |
| JPS5632578A (en) | 1981-04-02 |
| FR2463799A1 (fr) | 1981-02-27 |
| CH641828A5 (fr) | 1984-03-15 |
| GB2061994B (en) | 1984-08-15 |
| DE3028593A1 (de) | 1981-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4376715A (en) | Composition based on liquid crystal for electro-optical device | |
| US4428858A (en) | Composition based on liquid crystal for electro-optical device | |
| KR850000050B1 (ko) | 다색성 염료를 함유하는 액정조성물 | |
| EP0044893B1 (en) | Anthraquinone compounds and process for their preparation | |
| US4455253A (en) | Pleochroic anthraquinone dyes | |
| US4565424A (en) | Asymmetric dichroic dye molecules having poly(arylazo) linking groups, a bis-substituted aryl thiazyl end group, and another end group | |
| EP0098522B1 (en) | Liquid crystal composition | |
| US4232949A (en) | Liquid crystal compositions containing pleochroic dye | |
| US4472292A (en) | Liquid crystalline dielectric, new dichroitic naphthoquinone dyestuffs and electro-optical indicator element | |
| US4394070A (en) | Helichromic compounds and displays | |
| US4405211A (en) | Liquid crystal compositions with pleochroic anthraquinone dyes | |
| EP0087248B2 (en) | Liquid crystal composition containing azo dyes | |
| US4483594A (en) | Liquid crystal materials containing pleochroic anthraquinone dyes | |
| US4496221A (en) | Liquid crystal compositions with pleochroic anthraquines dyes | |
| US4356102A (en) | Dichroic liquid crystal compositions containing anthraquinone-based dyes | |
| US4358392A (en) | Liquid crystal-base composition for an electro-optical device | |
| Basturk et al. | Ester-substituted anthraquinone dyes soluble in nematic liquid crystal mixtures | |
| EP0098736A2 (en) | Anthraquinone dyes and liquid crystal compositions containing the dyes | |
| US4464282A (en) | Organic materials | |
| EP0044666B1 (en) | Helichromic compounds and displays | |
| EP0116218B1 (en) | Substituted anthracene-type isotropic dyes for liquid crystal display devices | |
| US4506957A (en) | Liquid crystal materials containing pleochroic anthraquinone dyes | |
| US4624532A (en) | Dichroic liquid crystal compositions containing anthraquinone-based dyes | |
| US4391754A (en) | Anthraquinone compounds | |
| US4883611A (en) | Dichroic coloring agents for liquid crystal displays |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| AS | Assignment |
Owner name: ETS S.A., FABRIQUES D`EBAUCHES, SCHILD-RUSTSTRASSE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:EBAUCHES S.A.;REEL/FRAME:004331/0137 Effective date: 19841023 |